Process for breaking petroleum emulsions



Patented July 18, 1944 UNITED STATES PATENT OFFICE PROCESS FOR BREAKING PETROLEUM EMULSIONS Melvin De Keiser, Webster Petrolite Corporation, corporation of Delaware Groote, University City, and Bernhard Groves,

Ltd, Wilmington, DeL, a

Mo., assignors to No Drawing. Application June 15, 1942, Serial No. 447,166

8 Claims.

This invention relates primarily to the resolution of petroleum emulsions. I

The main object of our invention is to provide a novel process for resolving petroleum emulsions cant value in removing impurities, particularly inorganic salts, from a pipeline oil.

We have discovered that if one oxyalkylates glycerol so as to introduce at least three oxyalkylene radicals for each hydroxyl group, and if the product so obtained is reacted with a polybasic carboxy acid having not over eight carbon atoms, and in such a manner as to yield a fractional ester, due to the presence of at least one free carboxyl radical, one can then esterify said acidic material or intermediate product with at least one mole of an alcoholic compound of the type herein described to give a variety of new compositions of matter which have utility in the I 'demulsification of crude oil.

The compounds herein contemplated may be produced in any suitable manner, but are usually manufactured by following one of two general procedures. In one of said procedures the oxyalkylated glycerol, which is, in essence, a polyhydric alcohol, is reacted with a polybasic acid so as to give an acidic material or intermediate product, which, in turn, is reacted with an alcoholic body of the kind hereinafter described, and momentarily indicated by the formula R1(OH)m.

Generically, the alcoholic body herein contemplated may be considered a member of the class in which m may vary from 1 to 10, although the Glycerol may be conveniently indicated by the following formula:

/OH CaHs-OH If treated with an oxyalkylating agent, and momentarily consideration will be limited to an oxyethylating agent, one may obtain an oxyethylated glycerol of the following formula type:

(CzHaOLuH in which the value of 11. may vary from 3 to 10 and all the values of n need not be identical. If a polybasic carboxy acid be indicated by the formula:

coon

R-COOH coon then the acyclic reaction product of one mole of oxyethylated glycerol and one mole of a polybasic carboiryv acid may be indicated by the following formula:

(cznimn-oocmcoom." CJHlOk-(CHiOLuH ozniown in which n" has the value of one or two. Similarly, if two moles of the polybasic acid be used,

then the compound may be indicated by the following formula:

Likewise, if three moles of a polybasic acid are employed, the compound may be indicated by the specific significance of m in the present instance will be hereinafter indicated. The second procedure is to react an alcohol of the formula type Rl(OH)m with a polybasic acid so as to produce an intermediate product, and then react said intermediate product or fractional ester with the selected oxyalkylated glycerol.

following formula:

(czrnowoocmcoonm CaHsO:-(CIH4O),. OOCR(COOHM" (cmlowoocmcoomn' If a fractional ester of the kind exemplified by the three preceding formulas is reacted with one or more moles of an alcohol of the kind previously described in a generic sense as R1(0H)m,

then obviously", one may obtain a material of the type indicated by the followingformula: [(C,H40)'.'O0CR(C0OH),."]=

cimorlwimowm.

in which a: i 1 or 2, y is 0, l or 2, and z is 1,2 or 3, and :r' is 0 or 1, and y is l or 2.

It has been previously stated that compounds of the type herein contemplatedmay be obtained by oxyalkylating agents, without being limited to ethylene oxide. Suitable oxyalkylating agents include ethylene oxide, propylene oxide, butylene oxide and glycid, which, although not included strictly speaking, by the unitary structure cnH ano is included within the meaning of the hereto appended claims and may be simply considered as in which n replaces the numbers 2, 3 or 4. Z includes the acidic hydrogen atom itself. In the above formula, and hereafter for convenience R1 is intended to include any hydroxyl groups that remain.

If the compounds herein contemplated are obtained under usual conditions, at the lowest temperatures, then the monomeric form is most like ly to result.

The production of the compounds herein contemplated is the result of one or more esterification steps. As is well known, esteriflcation procedures can be carried out in various manners, but generally speaking, esteriflcations can be carried out at the lowest feasible temperatures by' One procedure is to pass an inert driedgas through the mass to using one or several procedures.

be esterified, and have present at the same time a small amount of a catalyst, such as driedHCi Another gas, a dried sulfonic acid, or the like. and better procedure, in many instances, is to employ the vapors of a suitable liquid, so as to v remove any water formed and condense both the vapors of the liquid employed and the water in such a manner as to trap out the water and return-the liquid to the reacting vessel. cedure is commonly employed in the arts, and for convenience, reference is made to U. S. Patent No. 2,264,759, dated December 2, 1941, to Paul C. Jones. v r

Referring again to the last two formulas indicatin'g the compounds under consideration, it

can be readily understood that such compounds, in numerous instances, have the property of polyfunctionality.-

Thispro- In view of this fact, where there residual hydroxyl, one would expect that under suitable conditions, instead of obtaining the monomeric compounds indicated, one would in reality obtained a polymer in the sense, for example, that polyethylene glycols represent a polymer of ethylene glycol. The term polymer is frequentlyused to indicate the polymerized product derived from a monomer in which the polymer has the same identical composition as the monomer. In the present instance, however, polymerization involves the splitting and loss of water so that the process is essentially self-esterification. "I'hus, strictly speaking, the polymeric compounds are not absolutel isomers of the monomeric compounds, but since, for all practical pu poses, they can be so indicated, and since such practicevis common in the arts concerned with materials of this type, it is so adopted here.

Thus, reference in the appended claims to polyoxyethylene linkage, it is apparent that the ma.

terials herein contemplated may vary from compounds which are clearly water-soluble through self-emulsifying oils, to materials which are balsam-like and'sub-resinous or semi-resinous in nature. The compounds may vary from monomers to polymers, in which the unitar structure appears a number of times, for instance, 10 or 12 times. -It is to be noted that true resins, i. e., truly insoluble materials "of a. hard plastic nature, are not herein included. In other words, the polymerized-compounds are soluble to a fairly definite extent, for instance, at least 5% in some solvents, such as water, alcohol, benzene, dichloroethyl ether, acetone, cresylic acid, acetic acid, ethyl acetate, dioxane, or the like. This is simply another way of stating that the polymerized product contemplated must be of the sub-resinous type, which is commonly referred to as an A resin, or 'a B resin, as distinguished from a C resin, which is a highly infusible, insoluble resin (see Ellis, Chemistry of Synthetic Resins (1935),

. pages 862, et seq.) l

is at least one residual carboxyl and at least one Reviewing the form as presented, it is obvious that one may obtain compounds within the scope disclosed, which contain neither a, free hydroxyl.

nor a free carboxyl group, and one may also obtain a compound of the type in which there is present at least one free carboxyl, or at least one free hydroxyl, or both. The word "polar" has sometimes been used in the arts in this particular sense to indicate the presence of at least one free hydroxyl group, or at least one free carboxyl group, or both. In the case of the free'carboxyl group, the carboxylic hydrogen atom may, of

course, be replaced by any ionizable hydrogen atom equivalent, such, for example, as a metal,

an ammonium radical, a substituted ammonium nitol, sorbitol, various hexitols, dulcitol, pentaerythritol, sorbitan', mannitan, dipentaerythritol monoether, and other similar compounds.

Such particular types in which higher hydroxylated materials are subjected to oxyalkylation phthalic. Similarly,

and then employed in the same manner as oxyalkylatecl glycerol, is employed in the present in-- stance, are not contemplated in this specific case, although attention is directed to the same.

Reference is also made to other oxyalkylated compounds which may be used as reactants to replace oxyalkylated glycerol, or oxyalkylated ethylene glycol, which latter reactant is described in a co-pending application hereinafter referred to. The reactants thus contemplated include the type in which there is an amino or amido nitrogen atom, particularly when present in a low molal type of compound prior to oxyalkylation, reference being made to polyhydroxylated materials, including those having two or three hydroxyl groups, as well as those having more than three hydroxyl groups. For instance, the oxyalkylated derivatives, particularly the oxyethylated derivatives of ethyldiethanolamine, bis(hydroxyethyl)acetamide, the acetamide of tris(hydroxymethyl) aminomethane, tetrahydroxylated ethylene diamine, etc. Compounds may also be derived from cyclic diglycerol and the like.

Furthermore, for convenience, attention is directed to a somewhat similar class of materials which are described in our co-pending application Serial No. 401,384, filed July 7, 1941. now Patent No. 2,324,494, dated July 20, 1943. Said co-pending application involves the use of the same type of alcoholic bodies for reactants, but is limited, among other things, to the compounds which are essentially symmetrical in nature, for instance, involving the introduction of two alcoholic residues, whereas, in the present instance, one, two, or three, or more, might be introduced.

As indicated previously, the polybasic acids employed are limited to the type having not more than eight carbon atoms, for example, oxalic, malonic, succinic, glutaric, adipic, maleic, and one may employ acids such as fumaric, glutaconic, and various others, such as citric, malic, tartaric, and the like. The selection of the particular tribasic or dibasic acid employed, is usually concerned largely with the convenience of manufacture of the finished ester, and also the price of the reactants. Generally speaking, phthalic acid or anhydride tends to produce resinous materials, and greater care must be employed if the ultimate or final product be of a subresinous type.

preferred type of polybasic acid is such as to con- .tain six carbon atoms or less. Generally speaking, the higher the temperature employed, the easier it is to obtain large yields of esterifled product, althogh polymerization may be stimulated. Oxalic acid may be comparatively cheap, but it decomposes readily at slightly above the boiling point of water. For this reason it is more desirable to use an acid which is more resistant to pyrolysis. Similarly, when a polybasic acid is available in the form of an anhydride, such anhydride is apt to produce the ester with greater ease'than the acid itself. For this reason, maleic anhydride is particularly adaptable, and also, everything else considered, the cost is comparatively low on a per molar basis, even though somewhat higher on a per pound basis. Succinic acid or the anhydride has many attractive qualities of maleic anhydride, and this is also true of adipic acid. For purposes of brevity, the bulk of the examples, hereinafter illustrated, will refer to the use of maleic anhydride. although it is understood that any other suitable polybasic acid may be employed. Furthermore, reference Specifically, the

employed as reactants is concerned, it

is made to derivatives obtained by oxyethylation, although, as previously pointed out, other oxyalkylating agents may be employed.

As far as the range of .oxyethylated glycerols is our preference to employ those in which approximately to 24 oxyethylene groups have been introduced into a single glycerol molecule. This means that approximately five to eight oxyethylene radicals have been introduced for each original hydroxyl group.

The oxyalkylation of glycerol is a well-known procedure (see Example 11 of German Patent No. 605,973, dated November 22, 1934.-to I. G. Farbenindustrie Akt. Ges.) The procedure indicated in the following three examples is substantially identical with that outlined in said aforementioned German patent.

Omrmuan GLYCEROL Example 1 184 pounds of glycerol is mixed with /2%, by weight, of caustic soda solution having a specific gravity of 1.383. The caustic soda acts as a catalyst. The ethylene oxide is added in relatively small amounts. for instanqce, about 44 pounds at a time. The temperature employed is Example 2 The ratio of ethylene oxide is increased to 18 pound moles for each pound mole of glycerol. Otherwise, the same procedure is followed as in Example 1, preceding.

Oxxnrmaran Gmcasor. Example 3 The same procedure is followed as in the two previous examples, except that the ratio of ethylene oxide to glycerol is increased to 21 to one.

OXYETHYLA'IED GLYCEROL MALnAra Example 1 One pound mole of oxyethylated glycerol (1 to i Oxxnrnmran GLYCEROL Marmara Example 2 The same procedure is followed as in the preceding example, except that two moles of maleic anhydride are employed so as to obtain the dimaleate instead of the monomaleate.

OxYnrnYLArnn Gnxcaxor. Manners Example 3 The same procedure is followed as in the two erol (ratio 1 to 18) is substituted in place OXYETHYLATED GLYCEROL MALEATE Example '4 The same procedure is employed asin the preceding examples, except that oxyethylated glycof oxyethylated glycerol (ratio 1 to 15).

' OxYarHYLArnnGLYcERoL MALEATE Example 5 The same procedure is employed as in the preceding examples, except that oxyethylated glycerol (ratio 1 to 21-) is employed instead of oxyethylated glycerol (ratio 1 to 15) or (1 to '18).

Previous reference. has been made to an alcoholic body which has been defined generically by the formula R1(OH) m. The sub-generic class of alcoholic compounds employed as reactantsin the manufactureof the present compounds, are hydroxylated acylated diamides containing: (a) an acyl radical derived from a polybasic carboxy acid having not more than6 carbon atoms, and the acyl radical thereof linked to two amino nitrogen'atoms; (b) an acyl radical derived from a detergent-forming monocarboxy acid having at, least 8 and not more than 32 carbon atoms; and (c) an alcoholi-form hydroxyl radical.

. Detergent-forming. acids having at least 8 and not more than 32 carbon atoms are exemplified by fatty acids, naphthenic acids, abietic acids, oxidized parafiin or wax acids, or the like, or by simple modifications thereof, which do not detract from the ability of the acid to combine with alkali to produce soap or soap-like materials. As to oxidized petroleum acids, see U. S. Patent No;

2,242,837, dated May 20, 1941, to Shields.

- Thus, hydrogenated oleic acid, chlorinated naphthenic acid, or brominated abietic acid will form such detergent-forming bodies with the same ease as the parent materials themselves. The oxidized acids obtained by blowing or oxidation of the acids or esters, are satisfactory. Such acids have frequently been referred to collectively in the 'art as monocarboxy detergent-forming acids.

Needless to say, the acylatio'n need not be conducted by means 0f/the.aclditself, but may be conducted by means of any compound of the acid which contains the acid radical; for instance, an ester, an amide, an anhydride, an acyl chloride, etc.

It is our preference to use the fatty acids as the most desirable form of a detergent-forming acid, and particularly the unsaturated fatty acids, for instance, ricinoleic acid, oleic acid, mixed fatty acids derived from soyabean oil, rapeseed oil, sesame oil, cottonseed oil, corn oil, peanut oil, and the-like. Fatty acids such as lauric acid, myristic acid, palmitic acid, and the like, may be employed. The polybasic. carboxy acids which may be em-- ployed include oxalic acid, 'malonic acid, succinic acid, glutaric acid, adipic acid, tricarballylic acid, fumaric acid, maleic acid, aconitic acid, malic acid, tartaric acid, citric acid, etc. Such acids may be conveniently referred was low molal polybasic carboxy acids, or, more preferably, low

functional equivalent in supplying the acyl radical.

Suitable primary and secondary amines which may be used as primary reactants include the following hydroxylated types: monoethanolamine, ethyl ethanolamine, methyl ethanolamine, propanolamine, dipropanolamine, propyl propanolamine, etc. Other examples in; clude cyclohexylolamine, dicyclohexylolamine, cyclohexyl ethanolamine, cyclohexyl propanolamine, benzylethanolamine, benzylpropanolamine, pentanolamine, hexanolamine, octylethanolamine, octadecylethanolamine, cyclohexanolethanolamine, etc.

If the low molal polycarboxy acid happens to be hydroxylated, as in the instance of tartaric acid, citric acid, hydroxysuccinlc acid, and the like, it

is obvious that a hydroxylated' detergent-forming acid, for instance, ricinoleic acid, hydroxystearic acid, and the like, could be'esterified therewith, i, e., with the hydroxyl group which is part of the low molal acyl radical; and under such circumstances, the primary or secondary amine need not be hydroxylated. Under these circumstances, one might employ compounds such as amylamine, diamylamine, butylamine, dibutylamine, benzylamine, cyclohexylamine, etc. 7

, subsequently, reference will be made to U. S.

Patent No. 2,238,929, dated April 22, 1941, to

Cahn and Harris. Momentarily attention is directed to the numerous amino compounds, par- 'ticularly secondaryhydroxylated amines there employed in the manufacture of new compounds of the kind specifically contemplated in said Cahn and Harris patent. Said compounds are derived both from 10w molal monocarboxy acids and low molal polybasic carboxy acids.

Again attention is directed to the aforemen tioned Cahn, and Harris patent, insofar that it illustrates a large number of intermediate products. which may be utilized to produce various final compositions of matter, as, for example, sulfated or sulfonated derivatives,- as contemplated in said aforementioned U. S. .Patent' No. 2,238,929. However, the intermediate materials there described obviously can be used as alcoholic bodies in the preparationof compounds of the type herein contemplated. Such materials as there described are largely derivatives *of hydroxylated secondary amines; but for the purposes herein contemplated, such limitation does not exist in view of what has already been said. In the present instance, however, one is concerned with derivatives obtained from-low molal polybasic carboxy acids of'the kind described; and it is to be noted that, although many illustrations in the aforementioned Cahn and. Harris patent are concerned with low molal monocar-. boxy acids, the corresponding low molal polybasic carboxy acid compound is readily obtainable, al1 of which ,will be obvious. in view of what.

is said subsequently.

diethanolamine,

The following is substantially the manufacturing procedure set forth in the Cahn and Harris patent:

One can employ one pound mole of diethyl oxalate and two pound moles of monoet anolamine and react these compounds in a similar manner. This procedure yields a corresponding diamide of oxalic acid, along with the liberation of two pound moles of ethyl alcohol. Such bis- (hydroxyethyhoxalic acid diamide may be reacted with ricinoleic acid in the ratio of one pound mole of the diamide for 2 pound moles of ricinoleic acid. Similarly, a product can be obtained employing only one mole of ricinoleic acid for one mole of the diamide; ploy one mole of oleic acid and one mole of ricinoleic acid for each mole of the diamide. Similarly, diethanolamine may be employed with diethyl oxalate to give the corresponding tetra- (hydroxyethyl) oxalic acid diamide. Instead of diethyl oxalate, diethyl maleate, or numerous other reactants can be employed. Attention is called to the fact that hydroxylated polybasic carboxy acids might be employed in the same manner as hydroxyacetic acid can be employed in the analogous type of compound where a low molal monocarboxy acid is used.

By way of illustration, the following examples will serve:

HYDROXYLATED DIAMIDE TYPE INTERMEDIATE Example 1 One pound mole of a diamide of the followin type formula:

H o o /H \r- -li-n OHCzHl CzHAOH is esterified with one pound mole of ricinoleic acid until esterification is complete. Such esteriilcation reaction can be conducted by any one of the conventional means, usually heating at a temperature above the boiling point of water; for instance, 116-160 C. is suflicient. In some cases it may be desirable to pass a dried inert gas of water and xylene permitted to take place, and

the xylene returned to the reacting vessel while the water is diverted to a suitable draw-off connection.

HYDROXYLATED DIAMIDE TYPE INTERMEDIATE Example 2 One pound mole of oleic acid is substituted for one pound mole of ricinoleic acid in the preceding example.

HYDRoxYLATED DIAMIDE TYPE INTERMEDIATE Example 3 One pound mole of naphthenic acid is substituted for ricinoleic acid in Example 1, preceding.

HYDROXYLATED DIAMIDE TYPE INTERMEDIATE Example 4 Two pound moles of'ricinoleic acid are substior one might emtuted for one pound mole of ricinoleic acid in Example 1, preceding.

HYDROXYLATED DIAMIDE TYPE INTERMEDIATE Example 5 One pound mole of oleic acid is substituted for one pound mole of ricinoleic acid in Example 1, preceding.

HYDROXYLATED DIAMIDE TYPE INTERMEDIATE Example 6 The diamide derived from diethanolamine and diethyl oxalate of the following composition:

CzHaOH is substituted for the amide in Examples 1-5, preceding.

HYDROXYLATED DIAMIDE TYPE INTERMEDIATE Example 7 One pound mole of diethyl oxalate is reacted 011cm. 0 0' Canon Nsllrt Such reactant is employed in the manner suggested in Examples 1-5, preceding.

HYDRoxYLATED DIAMIDE TYPE INTERMEDIATE Example 8,

Monopropanolamine and dipropanolamine are employed to give compounds comparable to those described in Examples 1-7, preceding.

HYDRoxYLATED DIAMIDE TYPE INTERMEDIATE Example 9 One pound mole of diethyl oxalate is reacted with tris (hydroxymethyl) aminomethane to give a diamide of the following composition:

Such diamide is substituted in the previous examples, such as 1-5, inclusive.

HYDROXYLATED DIAMIDE TYPE INTERMEDIATE Example 10 Diethyl maleate is substituted for diethyl oxalate in Examples 1-9, preceding.

COMPLETED MoNoMEEIc DERIVATIVE Example 1 One pound mole of a product of the kind described under the heading Oxyethylated glycerol maleate, Example 1" is reacted with one pound mole of Hydroxylated diamide type intermediate, Example 1 preferably in the absence of any high boiling hydrocarbon or inert solvent. However, if an inert vaporizing solvent is employed, it is generally necessary to use one which has a boiling range than xylene, and sometimes removal of such solvent might present a difiicul "glycerol (ratio 1 to ample 4. preceding.)

appear as a constituent or ingredient of the final product. In any event, our preference is to conduct the reaction in, theabse'nce of any such,

solvent and permit the reaction to proceed with the elimination of water. The temperature of reactionis about 180 to 200 C. and time of reaction about hours.

'COMPLETED, MONOMERIG DERIVATIVE Example 2 The same procedure is followed as in Completed monomeric derivative, Example 1, preceding, except that the dimaleate described under the heading Oxyethylated glycerol maleate, Example 2 is used instead of the monomaleate.

COMPLETED MONOMERIC DERI ATIVE Example 3 The same procedureIis followed as in the two preceding examples, except that the trimaleate is substituted for the monomaleate'or dimaleate in the two preceding examples.

- -COMPLETED MONOMERIC DERIVATIVE Example 4 The same procedure is followed as in Examples 2 and 3, immediately preceding, except that for each pound mole of the maleata or each pound mole of the trimaleate, instead of using one pound mole of a hydroxylateddiamide of the kind employed in Examples 1 to 3, preceding as a reactant, one employs two pound moles.

' COMPLETED MONOMERIC DERIVATIVE Example;

, The same procedure is followed as in Example preceding, except that for each pound mole of trimaleate, instead of adding one pound mole of a hydroxylated diamide of the kind employed in Examples 1 to 3, preceding, one adds three pound moles of a hydroxylated diamide of the kind employed in Examples 1 to 3 for reaction.

CoMPL' rEn MONOHERIC DEiiIvArIVE Example 6 Reference to the preceding examples will show that'in each and every instance oxyethylated has been employed as a rawJmaterial or'primary reactant. In the pres-fa ent instance, a more highly oxyethylated glycerol is employed, to wit, one involving the ratio of 1 to 18. (See Oxyethylated glycerol maleate, Ex-

ComrLEr p MoxoMEnIc DERIVATIVE a, Example 7 The same procedure is followed as in Example 6, immediately preceding." except that the oxyethylated glycerolemployed represents one having an even higher degree of oxyethylation. For

' example, one indicated by the ratio of 1 to 21.

(See Oxyethylated glycerol maleate, Example 5, preceding.)

- COMPLETEDMONOMERIC DERIVATIVE Example 8 The same procedure is followed as in Examples 1 to 7, preceding, except that the hydroxylated intentional product.

instance.

sense previously described, particularly hastened by the diamide' employed is of the type exemplified by Hydroxylated type intermediate, Example 6.

conPLErEn Monomuuc DERIVATIVE Example 9 The same procedure is followed as in Examples 1 to 7, preceding, except that the hydroxylated diamide employed is of the type exemplified by I Hydroxylated type intermediate, Example 7.

CoMrLEI-En MONOMERIC DEnIvArIvE Example 10 The same procedure is followedasin Examples 1 to 7 preceding, except that the hydroxylated dlamide employed is of the type exemplified by Hydroxylated type intermediate, Example 9."

through the mixture. Sometimes it is desirable to add an esterification catalyst, such as, sulfuric acid, benzene sulfonic acid, or the like.

This is the same general procedure as employed in the manufacture of ethylene glycol dihydrogen diphthalate. (See U; S. Batent, No. 2,075,107, dated March 30, 1937, to Frasier.)

Sometimes esteriilcation is conducted most readily in the presence of an inert solvent, that carries away the water of esterification which may be formed, although as is readily appreciated, such water of esteriflcation is absent when such type of reaction involves an acid anhydride, such as maleic anhydride; and-a glycol. However, if water is formed, for instance. when .citric acid is employed, then a solvent such as xylene maybe present and employed to carry oi! the water formed. The mixture of xylene vapors and water vapors can be condensed so that the water is separated. The xylene is then returned meric materials and certain cogeneric by-prod ucts. This is typical, of course, of organic reactions of this kind, and as is well known, organic reactions per se are characterized by the fact that yields are the exception, rather than the rule, and that significant yields are satisfactory, especially in those instances where the .bY-Products or cogeners may satisfactorily serve with the same purpose as the principal or This is true in the present In many cases when the compound is manufactured for purposes of demulsification, oneis better of! to obtain a polymer in the polymer whose molecular weight is a rather sm instance, a polymer whose molecular weight is or six times the molecular weight of the monomer. Polymerization is presence of an alkali, and thus, in instances where it is necessary to have a maximum yield 01' the monomer, it may be necessary to takesuch precautions that the alkali I multiple of the molecular weight of the monomer, for

used in promoting oxyethylation of glycerol, be removed before subsequent reaction. This, of course, can be done in any simple manner by conversion to sodium chloride, sodium sulfate, or any suitable procedure.

In the preceding examples of the Completed monomeric derivative, Examples 1 to 10, inclusive, no reference is made to the elimination of such alkaline catalyst, in view ofthe effectiveness of the low multiple polymers as demulsifiers. Previous reference has been made to the fact that the carboxylic hydrogen atom might be variously replaced by substituents, including organic radicals, for instance, the radicals obtained from alcohols, hydroxylated amines, nonhydroxylated amines, polyhydric alcohols, etc. Obviously, the reverse is also true, in that a free hydroxyl group may be esterified with a selected acid, varying from such materials as ricinoleic acid to oleic acid, including alcohol acids, such as hydroxyacetic acid, lactic acid, ricinoleic acid and also polybasic acids of the kind herein contemplated.

With the above facts in mind, it becomes obvious that what has been previously said as to polymerization, with the suggestion that byproducts or cogeneric materials were formed, may be recapitulated with greater definiteness, and one can readily appreciate that the formation of heat-rearranged derivatives or compounds must take place to a greater ar lesser degree. Thus, the products herein contemplated may be characterized by being monomers of the type previously described, or esterification polymers, or the heat-rearranged derivatives of the same, and thus including the heat-rearranged derivatives of both the polymers and esteriflcation monomers, separately and jointly. Although the class of materials specifically contemplated in this instance is a comparatively small and narrow class of a broad genus, yet it is obviously impossible to present any adequate formula which would contemplate the present series in their complete ramification, except in a manner employed in the hereto appended claims.

Although the products herein contemplated vary so broadly in their characteristics, i. e., monomers through sub-resinous polymers, soluble products, water-emulsifiable oils or compounds, hydrotropic materials, balsams, subresinous materials, semi-resinous materials, and the like, yet there is always present the characteristic unitary hydrophile structure related back to the oxyalkylation, particularly the oxyethylation of the glycerol used'as the raw material. As hereinafter indicated, in the resolution of oil field emulsions, the demulsifier may be added to the emulsion at the ratio of 1 part in 10,000, 1 part in 20,000, 1 part in 30,000, or for that matter, 1 part in 40,000. In such ratios it well may be that one cannot differentiate between the solubility of a compound completely soluble in water in any ratio, and a semi-resinous product apparently insoluble in water in ratios by which ordinary insoluble materials are characterized. However, at such ratios the importance must reside in interfacial position and the ability to usurp, preempt, or replace the interfacial position previously occupied perhaps by the emulsifying colloid. In any'event, reviewed in this light, the obvious common property running through the entire series, notwithstanding variation in molecular size and physical makeup, is absolutely apparent. Such statement is an obvious over-simplification of the rationale underlying demulsiflcation, and does not even consider the resistance of an interfacial film to crumbling, displacement, being forced into solution, altered wettability, and the like. As to amidifioation polymers, for instance, where Z is a polyaminoamide radical, see what is said subsequently.

COMPLETED POLYMERIC DERIVATIVES INCLUnINC HEAT-REARRANGED COGENERS Example 1 A polyfunctional monomeric product of the kind described in Completed monomeric derivatives, Examples 1 to 7, preceding is heated at approximately 220-240 C., with constant stirring, for a period 2 to 60 hours, so as to eliminate suflicient water in order to insure that the resultant product has a molecular weight approximately twice that of the initial raw material.

COMPLETED POLYMERIC DERIVATIVES INCLUDING HEAT-REARRANGED COGENERS Example 2 The same procedure is followed as in the preceding example, except that polymerization is continued, using either a somewhat longer reaction time, 'or it may be, a somewhat higher temperature, or both, so as to obtain a material having a molecular weight of approximately three to four times that of the initial product.

COMPLETED POLYMERIC DERIVATIVES INCLUDING HEAT-REARRANGED COGENERS Example 3 COMPLETED POLYMERIC DERIVATIVES INCLUDING HEAT-REARRANGED COGENERS Example 4 The same procedure is followed as in Examples 1 to 3, preceding, except that one polymerizes a mixture instead of a single monomer, for instance, a mixture of materials of thekind described in Completed monomeric derivative, Example 3, and in Completed monomeric derivative, Example 4, are mixed in molecular proportion and subjected to polymerization in the manner indicated in the previous examples.

It is understood, of course, that the polymerized product need not be obtained as a result of a twostep procedure. In other words, one need not convert the reactants into the monomer and then subsequently convert the monomer into the polymer. The reactants may be converted through the monomer to the polymer in one step. Indeed, the formation of the monomer and polymerization may take place simultaneously. This is especially true if polymerization is conducted in the absence of a liquid such as xylene, as previously described, and if one uses a comparatively higher temperature, for instance, approximately 220 C. for polymerization. Thus, one pound mole of an oxyethylated glycerol polymaleate of the kind described in previous examples, is mixed with one pound mole of a polyhydroxylated material of the kind described under the heading Hydroxylated diamide type intermediate, Example 10, and reacted for 20 hours at approximately 200 C'runtil the mass is homogeneous. It is stirred constantly during reaction.

Polyfunct'ionality may reside in dehydration (etherization) of two hydroxyl groups attached to dissimilar molecules.

The factthat the polymerized and heat-rearranged products can be made in a single step, illustrates a phenomenon which sometimes occurs either in such instances where alcoholic bodies of the kind herein illustrated are contemplated as reactants, or where somewhat kindred alcoholic bodies are employed. Thefreactants may be mixed mechanically to give a homogeneous mixture, or if the reactants do not mix to give a homogeneous mixture, then early in the reaction stage there is formed, to a greater or lesser degree, suflicient monomeric materials so that a homogeneous system is present. Subsequently, as reaction continues, the system may become I heterogeneous and exist in two distinct phases,

one being possibly an oily body of moderate viscosity, and the other being a. heavier material, which is'stic y or sub-resinous in nature. In many instances it will be found that the thinner liquid material is a monomer and the more viscous or resinous material is a.polymer, as previously described. Such product can be used for de-' mulsiflcation by adding a solvent which will mutually dissolve the two materials, or else, by separating the two heterogeneous phases and employing each as if it were a separate product of reaction.

Conventional demulsifying agents employed in the treatment of oil field emulsions are used as such, or after dilution with any suitable solvent, such as water; petroleum hydrocarbons such as gasoline, kerosene, stove oil, a coal tar Product such as benzene, toluene, xylene, tar acid oil, cresol, anthracene oil, etc. Alcohols, particularly aliphatic alcohols, such as methyl alcohol, ethyl alcohol, denatured alcohoL-propyl alcohol, butyl alcohol, hexyl alcohol, octyl alcohol, etc., may be employed as diluents. Miscellaneous solvents, such, as pine oil, carbon tetrachloride, sulfur diat a somewhat flower cost than is possible with other available demulsiflers, or conventional mixtures thereof. It is believed that the particular demulsifying agent or treating agent herein described will find comparatively limited application, so far as the majorityof oil field emulsions are concerned; but we have found that such a demulsifying agent has commercial value, as it will economically break orresolve oil field emulsions in a number of cases which cannot be treated as easily or at so low a cost with the demulsifying agents heretofore available.

In practicing our improved process for resolving petroleum emulsions of the water-in-oil type, a treating agent or demulsifying agent of the kind above described is broughtinto contact with or caused to act upon the emulsion to be treated, in any of the various ways, or by any of the various apparatus now generally used to resolve or break petroleum emulsions with a chemical reagent, the above procedure being used either alone,or in combinationwith other demulsifying procedure, such as the electrical dehydration process.

The demulsifier herein contemplated may be,

tion, for instance, an iron reaction vessel speeds oxide extract obtained in the refining of petrole- I um, etc., may be employed as diluents. Similarly, the material or materials herein described, when employed as demulsiflers for water-in-oil emulsions may be admixed with one or more of the solvents customarily used in connection with conventional demulsifying agents, provided that such compounds are compatible. They will be compatible with the hydrophile type of solvent in all instances. Moreover, said material or materials may be used alone, or in admixture with other suitable well-known classes of demulsifying agents. I

It is well-known that conventional demulsifying agents may be used in a water-soluble form,

up reaction and polymerization, compared with a glass-lined vessel. v

- As has been previously indicated, the sub-genus employed as analcohol in the present instance is one of aseries of alcoholic compounds which are contemplated inour co-pending applications Serial Nos. 447,151, 447,152, 447,153, 447,154, 447,155, 447,156, 447,157, 447,158, 447,159, 447,160, 447,161, 447,162, 447,163, 447,164, 447,165, 447,167, and

447,168, filed June 15, 1942.

or in an oil-soluble form, or in a term exhibiting both oil and water-solubility. Sometimes they may be used in a form which exhibits relatively limited oil-solubility. However, since such reagents are sometimes used in a ratio of 1 to 10,000, or 1 to 20,000, or even 1 to 30,000, such an apparent insolubility in oil and water is not. significant, because said reagents undoubtedly have solubility within the concentration employed. This same fact is true in regard to the material or materials herein described, except that they are invariably water-soluble.

We desire to point out that the superiority of the reagent or demulsifying agent contemplated in our'herein described process for breaking petroleum emulsions, is based upon it 'ability to treat certain emulsions more advantageously and It is to be noted that in such instances where the alcoholic body contains a reactive amino hydrogen atom, for instance, in the case where an acylated hydroxylated polyamine is employed, for example, the ricinoleyl acid ester of hydroxyethyl ethylenediamine, the oxyethylated glycerol other way, in all appropriate instances, the expression esterification polymers in the appended claims, includes amidiflcation polymers, as well as esteriflcation polymers. 1

Having thus described our invention, what we claim as new and desire to secure by Letters Patent is:

1. A process for breaking petroleum emulsions comprising amember of the 'class consisting' of monomers, sub-resinous esterification polymers,

and cogeneric sub-resinous heat-rearranged derivatives of the'monomer and aforementioned polymers, separately and jointly, and of the fol-1 lowing formula:

in which R isthe carboxyl-free radical of a polyhydrogen atom equivalent including the acidic hydrogen atom itself; n represents'the numerals 2 to 4; n represents the numerals 3 to 10; n" represents the numerals 1 to 2; a: represents the numerals to 2; 11 represents the numerals 0 to 2; 2 represents the numerals 1 to 3; :n' represents the numerals 0 to 1; and y represents the numerals 1 to 2.

2. A process for breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of a demulsifier comprising a member of the class consisting of monomers, sub-resinous. -esterification polymers, and cogeneric sub-resinous heat-rearranged derivatives of the monomers and aforementioned polymers, separately and jointly, and of the following formula:

in which R is a carboxyl-free radical of a dibasic carboxy acid having not over 6 carbon atoms; R1 is a hydroxylated acylated diamide radical containing: (a) an acyl radical of a polybasic carboxy acid having not more than 6 carbon atoms and linked to two amino nitrogen atoms; and (b) an acyl radical of a detergent-forming monocarboxy acid having at least 8 and not more than 32 carbon atoms; Z is an acidic hydrogen atom equivalent including the acidic hydrogen atom itself; n represents the numerals 2 to 4; n represents the numerals 3 to :1: represents the numerals 0 to 2; 11 represents the numerals 0 to 2; and 2 represents the numerals 1 to 3.

,3. A process for breaking petroleum emulsions of the'water-in-oil type, characterized by subjecting the'emulsion to the action of a demulsifier comprising a member of the class consisting of monomers, sub-resinous esterification polymers, and cogeneric sub-resinous heat-rearranged derivatives of the monomers and aforementioned polymers, separately and jointly, and of the following formula:

in which R is a carboxyl-free radical of a dibasic carboxy acid having not over 6 carbon atoms; R1 is a hydroxylated acylated diamide radical containing: (a) an acyl radical of a polybasic carboxy acid having not morethan 6 carbon atoms and linked to two amino nitrogen atoms; and (b) an acyl radical of a detergent-forming monocarboxy acid having at least 8 and not more than 32 carbon atoms; Z is an acidic hydrogen atom equivalent including the acidic hydrogen atom itself; 11' represents the numerals 3 to 10; a: represents the numerals 0 to 2-; 11 represents the numerals 0 to 2; and 2 represents the numerals 1 to 3. a

4. A process for breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of a demulsinot more than 32' carbonatoms; Z is an acidic fiercomprising a polar member of the class consisting of monomers, sub-resinous esterification polymers, and cogeneric sub-resinous heat-rearranged derivatives of the monomers and aforementioned polymers, separately and jointly, and of the following formula:

[(oiHlmn-ooorzcooz C3H503"[(C1H40)11'H]! [(onnmtoocnooomh in which R is a carboxyl-free radical of a dibasi carboxy acid having not over 6 carbon atoms; F

is a hydroxylated acylated diamide radical con taining: (a) an acyl radical of a polybasic car boxy acid having not more than 6 carbon atom and linked to two amino nitrogen atoms; anc (b) an acyl radical of a detergent-forming monocarboxy acid having at least 8 and not more than 32 carbon atoms; Z is an acidic hydrogen atom equivalent including the acidic hydrogen atom itself; n represents the numerals 3 to 10; :2 represents the numerals 0 to 2; y represents the numerals 0 to 2; and 2 represents the numerals 1 to 3.

5. A process for breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of a demulsifler comprising a polar acidic member of the class consisting of monomers, sub-resinous esterification polymers, and cogeneric sub-resinous heat-arranged derivatives of the monomers and aforementioned polymers, separately andjointly, and of the following formula:

in which R is a carboxyl-free radical of a dibasic carboxy acid having not over 6 carbon atoms; R; is a hydroxylated acylated diamide radical containing: (a) an acyl radical of apolybasic carboxy acid having not more than 6 carbon atoms and linked to two amino nitrogen atoms; and (b) an acyl radical of a detergent-forming monocarboxy acid having at least 8 and not more than 32 carbon atoms; Z is an acidic hydrogen atom equivalent including the acidic hydrogen atom itself; n represents the numerals '3 to 10; a: rep resents the numerals 0 to 2; 11 represents the numerals 0 to 2; and z represents the numerals 1 to 3.

6. A process for breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of a demulsifier. comprising a polar acidic member of the class consisting of monomers, sub-resinous esterification polymers, and cogeneric sub-resinous heatrearranged derivatives of the monomers and aforementioned polymers, separately and jointly, and of the following formula:

in which R is a carboxyl-free radical of a dibasic carboxy acid having not over 6 carbon atoms; R1 is a hydroxylated acylated diamide radical containing (a) an acyl radical of a polybasic carboxy acid'h-aving not more than 6 carbon atoms and linked to two amino nitrogen atoms; and (b) an acyl radical of a higher fatty acid having at least 8 and not more than 32 carbon atoms; Z is an acidic hydrogen atom equivalent including theacidic hydrogen atom itself; n represents the numerals 3 to 10; .1: represents the numerals 0 to 2; 11 represents the numerals 0 to 2; and z represents the numerals l to 3.

7. A process for breaking petroleum emulsions of the water-in-oil type. characterizedby subjecting the emulsion to the action of a demulsi- .fier comprising a polar acidic member of the class consisting of monomers, sub-resinous esterification polymers, and cogeneric sub-resinous heat-rearranged derivatives of the monomers and aforementioned polymers, separately and jointly, and of the following formula:

l (cinio).. oocRcooz]z cur oswanna l(cinlo).. oocn cooall." in which R is a carboxyl-free radical of a dibasic carboxy acid having not over 6 carbon atoms; R1 is a hydroxylated acylated diamide radical containing (a) an acyl radical of a polybasic car-boxy acid having not more than 6 carbon atoms and linked to two amino nitrogen atoms; and (b) a higher fatty acid having 18 carbonatoms; vZ is an acidic hydrogen atom equivalent including the acidic hydrogen atom itself; n represents the numerals 3 to 10; :1: represents the numerals 0 to 2; 1/ represents the numerals 0 to 2; and 2 represents the numerals, 1 to 3.

8. A' process for breaking petroleum emulsions of the water-in-oii type, characterized by subjecting the emulsion to the action of a demulsifler comprising a polar acidic member of the class consisting of monomers, sub-resinous esteriflca- 7 -carboxy acid having not more than 6 carbon atoms and linked to two amino nitrogen atoms:

and (b) a ricinoleyl radical; Z is an acidic hydrogen atom equivalent including the acidic hydrogen atom itself; n representsthe numerals 3 to 10,; 2: represents the numerals 0 to 2; 1! repsents the numerals 0 to '2; and z represents the numerals 1 to 3.

MELVIN DE GROOTE.

BERNHARD KEISER. 

